U.S. patent number 4,297,145 [Application Number 06/178,159] was granted by the patent office on 1981-10-27 for silane/filler preparations, process for their production and their use.
This patent grant is currently assigned to Degussa Aktiengesellschaft. Invention is credited to Heinz Grewatta, Lothar Rothbuhr, Siegfried Wolff.
United States Patent |
4,297,145 |
Wolff , et al. |
October 27, 1981 |
Silane/filler preparations, process for their production and their
use
Abstract
The invention relates to a silane/filler preparation, consisting
essentially of from 5 to 70% by weight of at least one silane
corresponding to the following formula in which X=a halogen atom,
preferably chlorine or bromine, p=1 or 2, m=1 to 5, R.sup.1 =a
C.sub.1 -C.sub.5 alkyl group, C.sub.5 -C.sub.8 -cycloalkyl group or
a phenyl group, R=a C.sub.1 -C.sub.5 -alkyl group, a C.sub.5
-C.sub.8 -cycloalkyl group, a phenyl group, a benzyl group or a
C.sub.1 -C.sub.5 -alkoxy-C.sub.1 -C.sub.5 -alkyl group, and n=0, 1
or 2, and--respectively balanced to 100%--from 95 to 30% by weight
of at lesat one inorganic filler, preferably carbon black and
silicate fillers as, e.g., silica. There is also disclosed a
process for the production of the silane/filler preparation and its
use in optionally cross-linkable polymeric moulding compositions or
vulcanizable or cross-linkable rubber moulding compositions such as
sulphur-vulcanizable moulding compositions based on natural rubber
and/or synthetic rubber.
Inventors: |
Wolff; Siegfried
(Bornheim-Merten, DE), Rothbuhr; Lothar
(Hurth-Hermulheim, DE), Grewatta; Heinz (Cologne,
DE) |
Assignee: |
Degussa Aktiengesellschaft
(Frankfurt, DE)
|
Family
ID: |
6078679 |
Appl.
No.: |
06/178,159 |
Filed: |
August 14, 1980 |
Foreign Application Priority Data
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Aug 17, 1979 [DE] |
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2933346 |
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Current U.S.
Class: |
106/475; 106/482;
106/486; 524/263 |
Current CPC
Class: |
C04B
20/1051 (20130101); C08K 9/06 (20130101) |
Current International
Class: |
C04B
20/00 (20060101); C08K 9/00 (20060101); C08K
9/06 (20060101); C04B 20/10 (20060101); C09C
001/28 () |
Field of
Search: |
;106/307,38Q
;260/42.15,763 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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2542534 |
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Sep 1975 |
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DE |
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2528134 |
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Jan 1976 |
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DE |
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2255577 |
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Jul 1976 |
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DE |
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2536674 |
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Feb 1977 |
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DE |
|
2747277 |
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Apr 1979 |
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DE |
|
1592861 |
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May 1979 |
|
DE |
|
Primary Examiner: Poer; James
Attorney, Agent or Firm: Cushman, Darby & Cushman
Claims
What is claimed is:
1. A silane/filler preparation, consisting essentially of from 5 to
70% by weight of at least one silane corresponding to the following
formula
in which
X=a halogen atom
p=1 or 2,
m=1 to 5,
R.sup.1 =a C.sub.1 - to C.sub.5 -alkyl group, a C.sub.5 - to
C.sub.8 -cycloalkyl group or the phenyl group,
R=a C.sub.1 - to C.sub.5 -alkyl group, a C.sub.5 - to C.sub.8
-cycloalkyl group, the phenyl group, the benzyl group or a C.sub.1
- to C.sub.5 -alkoxy-C.sub.1 - to C.sub.5 -alkyl group, and
n=0, 1 or 2,
and--respectively balanced to 100%--from 95 to 30% by weight of at
least one inorganic filler based on the two components.
2. A silane/filler preparation as claimed in claim 1 where R is a
C.sub.1 - to C.sub.5 -alkyl group, a C.sub.5 - to C.sub.8
-cycloalkyl group, a phenyl group or a benzyl group.
3. A silane/filler preparation as in claim 2 wherein X is chlorine
or bromine.
4. A silane/filler preparation as in claim 3 wherein the filler is
carbon black or a silicate filler.
5. A silane/filler preparation as claimed in claim 4 wherein the
inorganic filler is carbon black.
6. A silane/filler preparation as claimed in claim 5 wherein the
carbon black is a furnace black having a specific surface area of
from 30 to 140 m.sup.2 /g and a mean primary particle size of from
20 to 60 nm.
7. A silane/filler preparation as claimed in claim 4 wherein the
inorganic filler is a silica filler produced pyrogenically or by
precipitation in aqueous medium.
8. A silane/filler preparation as claimed in claim 7 wherein the
silica filler is a silica filler having a specific surface area of
from 100 to 250 m.sup.2 /g and a mean primary particle size of from
10 to 400 nm.
9. A silane/filler preparation as claimed in claim 7 wherein the
silica filler is one which has been hydrophobised with at least one
silane.
10. A silane/filler preparation as claimed in claim 3 wherein the
inorganic filler is a natural light filler suitable for use in
rubber technology.
11. A silane/filler preparation as claimed in claim 10 wherein the
natural light filler is kaolin, clay, chalk, siliceous chalk or
diatomaceous earth.
12. A process for the production of a silane/filler preparation
which comprises introducing at least one carbon black and/or at
least one silicate filler in powder form into a powder mixer in a
quantity of from 95 to 30% by weight, after which at least one
liquid silane corresponding to the following formula
in which
X=a halogen atom
p=1 or 2,
m=1 to 5,
R.sup.1 =a C.sub.1 - to C.sub.5 -alkyl group, a C.sub.5 - to
C.sub.8 -cycloalkyl group or the phenyl group,
R=a C.sub.1 - to C.sub.5 -alkyl group, a C.sub.5 - to C.sub.8
-cycloalkyl group, the phenyl group, benzyl group or a C.sub.1 - to
C.sub.5 -alkoxy-C.sub.1 - to C.sub.5 -alkyl group, and
n=0, 1 or 2,
is added in a quantity of from 5 to 70% by weight, respectively
balanced to 100% relative to the filler, followed by brief
intensive mixing until a powder-form or granular free-flowing
preparation is formed.
13. A process as claimed in claim 12 wherein the silane is sprayed
onto the particles of the filler in motion in the powder mixer.
14. A process as claimed in claim 12 wherein the silane is applied
in solution or suspension to the particles of the filler in motion
in the powder mixer.
15. A silane/filler preparation as claimed in claim 4 wherein n is
0.
16. A silane/filler preparation as claimed in claim 15 where R is a
C.sub.1 - to C.sub.5 -alkyl group.
17. A silane/filler preparation as claimed in claim 16 where p is
1.
18. A silane/filler preparation as claimed in claim 17 where the
silane is 3-chloropropyl triethoxysilane.
19. A moulding composition comprising a silane/filler of claim 1
and a mouldable polymer.
20. A moulding composition according to claim 19 which is
vulcanisable.
21. A vulcanisable or cross-linkable rubber moulding composition
comprising a silane/filler of claim 1 and a vulcanisable or
cross-linkable rubber.
22. A composition according to claim 21 wherein the rubber is a
sulphur vulcanisable natural rubber or synthetic rubber.
23. A composition according to claim 22 wherein the rubber is
natural rubber, a polybutadiene, polyisoprene, butadiene-styrene
copolymer, butadiene-acrylonitrile copolymer, polychlorobutadiene,
butyl rubber, chlorobutyl rubber, bromobutyl rubber, or
ethylene-propylene-non-conjugated polyene terpolymer.
Description
BACKGROUND OF THE INVENTION
This invention relates to powder-form or granular silane/filler
preparations which are used in particular in vulcanisable rubber
moulding compositions based on natural or synthetic rubbers or
blends thereof which contain at least one synthetic or natural
silicate filler and/or carbon black.
Powder-form mixtures of oligosulphidic silanes and silicate fillers
are already known (German OS No. 22 55 577 and related Thurn U.S.
Pat. No. 3,873,489), as are powder-form mixtures of mercaptosilanes
and silicate fillers (German AS No. 25 28 134). Mixtures of carbon
black and oligosulphidic silanes (German OS No. 27 47 277 and
related Wolff U.S. Pat. No. 4,128,438) are also known. The entire
disclosures of the Thurn and Wolff U.S. patents are hereby
incorporated by reference and relied upon. All these mixtures are
eminently suitable for use in rubber moulding compositions and the
alkoxy silanes used therefor are of the type which contain sulphur
bound to carbon. This sulphur plays a noticeable part in the
vulcanisation reaction.
SUMMARY OF THE INVENTION
It was all the more surprising then to discover, as applicants have
done, that halogen alkyloxysilanes, of which the typical
representative is 3-chloropropyl triethoxy silane (Cl-PTES in
short), also produced valuable effects in rubber moulding
compositions and valuable property improvements in their
vulcanisates. Thus, mixtures and moulding compositions based on
halogen rubbers containing silicate fillers and halogen silanes of
the type in question have already been proposed. It was even more
surprising to find, as has now been found, that these silanes
produce unexpected effects of an advantageous nature, even in
silicate-filled moulding compositions based on the most common
halogen-free rubbers, and also surprising improvements in the
properties of the vulcanisates.
In the light of previous experience and in view of the prior art
referred to above, it was even less to be expected that, according
to the present invention, some important properties of the rubber
mixtures and their vulcanisates can be improved even further by
using a silane/filler preparation for the production of the
moulding compositions rather than using the silane and the filler
separately in the production of the mixtures.
The present invention provides a silane/filler preparation,
consisting of from 5 to 70% by weight of at least one silane
corresponding to the following formula
in which
X=a halogen atom, e.g., fluorine or iodine but preferably chlorine
or bromine,
p=1 or 2,
m=1 to 5,
R.sup.1 =a C.sub.1 - to C.sub.5 -alkyl group, C.sub.5 - to C.sub.8
-cycloalkyl group or a phenyl group,
R=a C.sub.1 - to C.sub.5 -alkyl group, a C.sub.5 - to C.sub.8
-cycloalkyl group, a phenyl group, a benzyl group or a C.sub.1 - to
C.sub.5 -alkoxy-C.sub.1 - to C.sub.5 -alkyl group, and
n=null, 1 or 2,
and--respectively balanced to 100%--from 95 to 30% by weight of at
least one inorganic filler.
The preparations according to the invention are granular or
powder-form preparations which are stable in storage and, in
general, also stabilise the hydrolysis-sensitive alkoxy silanes in
the preparations, which in addition--in contrast to the liquid or
powder-form starting materials--are present in a non-dust-forming,
readily processible aggregate state convenient to the processor
(rubber-processing industry) and which, most importantly, produce
valuable effects in rubber mixtures based on natural and/or
synthetic rubbers with or without halogens in the molecule which
are filled e.g. with silicate fillers and, advantageously, with
carbon black. These effects and improvements in the properties of
the vulcanisates produced by the silane/filler preparations
according to the invention, which in some instances are synergistic
effects in relation to the separate addition of silane and filler
to the other constituents of the mixture, are explained further
below and, in particular, in the Examples.
Carbon blacks which are eminently suitable for the purposes of the
invention include the types known per se, particularly the
so-called rubber blacks used in the rubber-processing industry,
preferably furnace blacks, such as HAF- and ISAF-carbon blacks, and
the commercially available powder-form Printex.RTM. carbon blacks
manufactured by DEGUSSA with specific surfaces, as measured by the
nitrogen absorption method according to DIN No. 66 132 (German
Industrial Standard 66132), of from about 30 to 140 m.sup.2 /g and
mean primary particle sizes (arithmetic mean) of from about 20 to
60 nanometers. Mixtures of different carbon blacks may also be used
for producing the preparations according to the invention, for
example mixtures of Printex.RTM. 60 and Printex.RTM. 300 or
mixtures of Printex.RTM. 30 and Printex.RTM. 300. Powder-form
products or free-flowing non-tacky granulates are obtained,
depending on the production process used and the mixing ratio
within the claimed quantitative ratios of silane to carbon
black.
Suitable synthetic inorganic fillers are primarily the reinforcing
fillers and used in the rubber industry, particularly the
commercially available powder-form pyrogenic or precipitated
silicas manufactured by Degussa, such as Aerosil.RTM.,
Ultrasil.RTM. VN 3, Ultrasil.RTM. VN 2, Silteg.RTM. AS 9,
Silteg.RTM. AS 7, Durosil.RTM. and Extrusil.RTM., with specific
surface areas (see DIN No. 66 132) of from about 20 to 400 m.sup.2
/g, preferably from 100 to 250 m.sup.2 /g, and mean primary
particle sizes of from about 10 to 400 nanometers. Mixtures of
these various silicas may also be used for producing the
preparations according to the invention.
Natural inorganic fillers are also suitable for the purposes of the
invention, examples being kaolins, clay, chalk, siliceous chalk,
diatomaceous earth (kieselguhr), finely powdered quartz sands and
asbestoses. It is also possible to use fillers in the form of mixed
oxides or oxide mixtures of silicon dioxide with the oxides of the
metals aluminium, magnesium, calcium, barium, zinc and/or
titanium.
The inorganic fillers can also have been hydrophobised in known
manner with silanes of which typical representatives are Degussa's
commercial products e.g. AEROSIL.RTM. R 972 (based on pyrogenic
silica) and SIPERNAT.RTM. D 17 (based on precipitated silica).
Synthetic silicates, for example aluminium silicates or
alkaline-earth metal silicates, such as magnesium or calcium
silicate, with specific surface areas of from about 20 to 400
m.sup.2 /g and primary particle sizes of from about 10 to 400 nm
may also be used.
Filler mixtures, such as silica/kaolin or silica/kieselguhr/chalk
and blends of the silicate-containing reinforcing fillers with the
known rubber-grade carbon blacks, for example silica/HAF-carbon
black or silica/kaolin/ISAF-carbon black, may also be successfully
used for producing the preparations according to the invention.
The halogen alkoxysilanes corresponding to formula I, which are
present in the preparations according to the invention in
quantities of from 5 to 70% by weight, preferably in quantities of
from 15 to 60% by weight and advantageously in quantities of 50% by
weight, include in particular the following silanes: chloromethyl
trimethoxysilane, chloromethyl triethoxysilane, bromomethyl
triethoxysilane, dichloromethyl triethoxysilane, 1-chloro-1-methyl
methyl trimethoxy silane, 2-chloroethyl trimethoxy silane,
2-bromoethyl trimethoxy silane, 2-dibromoethyl trimethoxy silane,
3-bromopropyl trimethoxysilane, 3-chloropropyl trimethoxysilane,
3-dichloropropyl trimethoxysilane, 3-chloropropyl triethoxysilane,
3-bromopropyl triethoxy silane, 3-dibromopropyl triethoxysilane,
2-bromo-1-methyl-ethyl tripropoxysilane, 2-dichloroethyl
tri-n-butoxy silane, 2-chloroethyl tri-2-methyl propoxysilane,
3-bromopropyl tri-t-butoxy silane, 3-dibromopropyl
triisopropoxysilane, 3-bromopropyl tri-n-pentoxysilane,
5-chloropentyl trimethoxysilane, 2-iodoethyl trimethoxysilane,
2-chloroethyl tri-2'-ethyl-ethoxysilane, 2-bromo-2-methyl-ethyl
dimethoxyethoxy silane, 3-dichloropropyl methoxy-ethoxy-propoxy
silane, 3-chloropropyl dimethoxy methyl silane, 3-bromopropyl
diethoxy ethyl silane, 3-chloropropyl ethoxy diethyl silane,
3-bromopropyl tris-(1-methoxyethoxy)-silane, 3-chloropropyl
diethoxy phenyl silane, 3-dichloropropyl dimethoxycyclopentyl
silane, 3-bromopropyl di-n-propoxy cyclohexyl silane,
3-chloropropyl dicyclohexoxy cyclohexyl silane, 3-bromopropyl
diethoxy cycloheptyl silane, 3-chloropropyl ethoxyphenyloxyethyl
silane, 3-dibromopropyl benzyloxyethoxyethyl silane,
4-chloro-n-butyl trimethoxysilane, 4-bromo-n-butyl
trimethoxysilane, 3-chloro-2-methyl propyl trimethoxysilane,
3-chloro-3-methyl propyl cyclo-octyl dipropoxysilane,
3-chloro-2-ethyl-propyl diethoxymethylsilane,
3-bromo-3-ethyl-propyl dimethoxymethylsilane, 3-chloro-2-methyl
propyl dimethoxyphenylsilane, 5-chloro-n-pentyl triethoxy silane,
4-bromo-1-methyl-butyl-cyclooctoxy dimethoxysilane,
4-bromo-2-methyl-butyl triethoxysilane, 2-chloro-2-methyl-ethyl
tripentoxysilane, 2-dichloro-2 -methyl-ethyl tributyloxysilane,
3-bromopropyl triphenoxysilane, 3-chloropropyl tribenzyloxysilane,
3-dibromopropyl tricyclopentoxysilane, 3-bromopropyl
tri-ni-pentoxysilane, dibromomethyl triethoxysilane, dichloromethyl
triethoxysilanes, 2-dichloroethyl triethoxysilane, 2-dibromoethyl
tri-n-propoxysilane, 3-dichloropropyl triethoxysilane,
2-dichloro-i-propyl triethoxysilane, 2-dibromo-i-propyl
tri-i-propoxysilane, 3-dichloropropyl tri-n-propoxysilane,
3-dibromopropyl tri-n-butoxysilane, 4-dichlorobutyl
triethoxysilane, 4-dibromobutyl tri-n-propoxysilane,
5-dichloropentyl triethoxysilane, 5-dibromopentyl
tri-n-propoxysilane and mixtures of these halogen alkyloxysilanes.
It is preferred to use those halogen alkyloxysilanes which contain
one halogen atom (p=1 in formula I) and three alkoxysilyl groups
and mixtures thereof.
The silanes corresponding to formula I can be obtained by method
known per se, for example from halogen silanes still containing at
least one hydrogen atom, by catalytically controlled addition with
a halogenated hydrocarbon containing a C-C-double bond
(hydrosilylation). The halogen atom(s) situated on the silicon atom
are then converted into alkoxy silanes again in known manner, for
example, by alcoholysis. It has been found that the crude silanes
emanating from production may be directly used with success for the
purposes of the invention providing they are substantially free
from hydrolysable halide and hydrogen halide. If present, these
impurities are removed by treatment with ammonia or sodium hydride,
optionally followed by rectification.
The preparation is produced in high-speed mixers known per se, such
as powder mixers, propeller mixers or bead-forming and granulating
machines.
The present invention also relates to the process for producing the
silane/filler preparations described above. In this process at
least one carbon black and/or at least one inorganic filler in
powder form is introduced into a powder mixer in a quantity of from
95 to 30% by weight, at least one liquid silane corresponding to
formula I is then added in a quantity of from 5 to 70% by weight,
respectively balanced to 100% relative to the filler, followed by
brief intensive mixing until a powder-form or granular,
free-flowing preparation is formed.
The silanes may with advantage be sprayed onto the particles of the
filler(s) in motion in the powder mixer. Alternatively, they are
applied in solution or suspension to the particles of the filler(s)
in motion in the powder mixer.
The compositions can comprise, consist essentially of or consist of
the stated material.
Unless otherwise indicated all parts and percentages are by
weight.
DETAILED DESCRIPTION OF THE INVENTION
Production Examples
Example 1
The inorganic filler used is a carbon black having the following
test data (Printex.RTM. 30, a product of Degussa A. G., D-6000
Frankfurt-am-Main):
______________________________________ Nitrogen surface area
according to DIN 66 132 78 m.sup.2 /g Mean primary particle size 27
nm pH-value (DIN 53 200) 9 Dibutyl phthalate absorption according
to DIN 53 601 100 ml/100 g
______________________________________
10 kg of the above-defined carbon black were weighed into a
trough-shaped powder mixer 150 liters in capacity equipped with a
propeller-like mixing tool, 10 kg of 3-chloropropyl triethoxysilane
were then added and the mixture components processed with one
another and homogenised for 30 seconds at 360 r.p.m. The apparatus
used is described in German AS No. 15 92 861. After withdrawal of
the discharge unit, 20 kg of a granulate having a mean particle
diameter of 1.0 mm are removed. The granulate thus produced was
dust-free, non-tacky, free-flowing, stable on storage and easily
meterable and could readily be mixed in in the production of rubber
moulding compositions.
Example 2
The filler used for this Example was a silica filler (Ultrasil.RTM.
VN 3, a DEGUSSA product) characterised by the following test
data:
______________________________________ Nitrogen surface area
according to DIN 66 132 165 to 180 m.sup.2 /g Conductivity of a
4.0% 1000 .mu.S/cm suspension in water (S = Siemens) pH-value
according to DIN 53 200 6.3 Water content 5.0% by weight
______________________________________
10 kg of the silica filler are introduced into the same
trough-shaped powder mixer as described in Example 1. 10 kg of
3-chloropropyl triethoxysilane are then sprayed into the mixer.
After spraying in, the two components are intensively mixed for
another 20 seconds at 360 r.p.m. Thereafter, the discharge unit of
the mixer is opened and a homogeneous powder-form mixture of the
two components is removed.
Example 3
The inorganic filler used in this case was natural aluminium
silicate (clay) characterised by the following data:
______________________________________ Sieve residue according to
DIN 53 580 43 .mu.m sieve 0.05% Mean particle size 2 .mu.m Nitrogen
surface area according to DIN 66 132 30 m.sup.2 /g pH-value
according to DIN 53 200 5.5
______________________________________
17 kg of the natural aluminium silicate characterised above were
introduced into the powder mixer described in Example 1, 3 kg of
3-chloropropyl triethoxysilane were added, followed by intensive
mixing for 20 seconds. Thereafter the discharge valve was opened
and a homogeneous, powder-form mixture of the two components was
discharged with the mixing tool rotating.
The preparations according to the invention can be used in moulding
compositions based on optionally cross-linkable polymers, such as,
in particular, thermoplastic polymer, which contain silicate
fillers and/or carbon black as filler. Polymers such as these
include inter alia polyolefins, such as polyethylene,
polypropylene, ethylene-propylene copolymers, etc.
The preparations are preferably used with good and unexpected,
advantageous results in compositions and moulding compositions
based on natural and synthetic rubbers filled with silicate fillers
and, optionally, with carbon black. The rubbers include in
particular natural rubbers, polybutadiene rubbers, polyisoprene
rubbers, butadiene-styrene rubbers, butadiene-acrylonitrile
rubbers, butyl rubbers, terpolymers of ethylene, propylene and
unconjugated dienes, e.g., cyclooctadiene, norbornadiene,
cyclododecatriene or dicyclopentadiene, carboxyl rubbers, epoxide
rubbers and trans-polypentenamers, also halogen rubbers such as,
for example, halogenated butyl rubbers, particularly brominated or
chlorinated butyl rubbers, chlorinated rubbers, rubber
hydrochlorides and, in particular, the polymers of
2-chloro-1,3-butadiene, also chloro-sulphonated polyethylene,
ethylene-propylene co-polymers, ethylene-vinyl acetate copolymers,
chemical derivatives of natural rubber and modified natural
rubbers. Blends of these rubbers may also be used.
In addition to the fillers, the rubber moulding compositions
contain the usual constituents, such as cross-linkers,
accelerators, antiagers, plasticisers or plasticiser oils, also
aliphatic acids such as, for example, stearic acid, metal oxides
such as zinc oxide, magnesium oxide and/or lead oxide, optionally
sulphur, stabilisers against ageing, fatigue, ozone and/or light
and optionally oligosulphidic silanes (Thurn U.S. Pat. No.
3,873,489 or DE-PS No. 25 42 534 or related Pletka U.S. Pat. No.
4,072,701) which may even replace sulphur as cross-linking agent.
DE-PS No. 25 36 674 or related Pletka U.S. patents and the Wolff
U.S. application Ser. No. 034,203 of Apr. 27, 1979 are hereby
incorporated by reference and relied upon.
The rubber moulding compositions are produced by methods known per
se. In the following Application Examples, the quantities in which
the mixture components are used are given in parts by weight (PW).
The respective comparison mixtures are identified by the letter "V"
before the number. The corresponding mixtures containing the
preparations according to the invention are identified by the
letter "E".
APPLICATION EXAMPLES
Example 4
The following moulding compositions or mixtures based on
styrene-butadiene rubber (SBR 1500) demonstrate the advantageous
use of silane/filler preparations according to the invention with
synergistic effect:
______________________________________ Mixture No. (quanities in
parts by weight) Constituents V4.1 V4.2 V4.3 V4.4 E4.1 E4.2
______________________________________ SBR 1500 100 100 100 100 100
100 Zinc oxide (see Example 1) 4 4 4 4 4 4 Stearic acid 2 2 2 2 2 2
Silica filler (see Example 2) 50 50 50 50 50 42.5 HAF-carbon black
N330 -- -- 7.5 7.5 -- -- Cl-PTES purified with ammonia -- 7.5 --
7.5 -- -- Preparation carbon black/Cl-PTES.sup.1 Preparation silica
-- -- -- -- 15 -- -- -- -- -- -- 15 filler/Cl-PTES.sup.2
N-cyclohexyl- 2-benzothiazole sulphenamide 1.5 1.5 1.5 1.5 1.5 1.5
Sulphur 2 2 2 2 2 2 ______________________________________ .sup.1
1:1 mixture of HAFcarbon black and ClPTES according to Example 1
.sup.2 1:1 mixture of silica filler and ClPTES according to
Exmample 2
The six mixtures were tested in accordance with the known
Standards. The relevant test results are set out in the following
Table (vulcanisation temperature=160.degree. C.).
__________________________________________________________________________
V4.1 V4.2 V4.3 V4.4 E4.1 E4.2
__________________________________________________________________________
Vulcanisation time 85 80 80 80 80 80 Tensile Strength (in MPa) 16.2
18.7 18.5 16.2 17.7 17.7 Modulus 200 (in MPa) (see DIN 53 504) 2.5
5.9 3.5 5.1 6.1 7.0 Modulus 300 (in MPa) (see DIN 53 504) 4.5 11.3
6.2 10.4 12.2 13.9 Breaking elongation (in %) 620 390 550 340 370
340 Shore hardness (DIN 53 505) 62 69 70 72 72 69 Wear (DIN 53 516)
133 91 118 93 91 91 Rheometer test (DIN 53 529 Provisional)
D.sub.min (in NM) 1.90 1.36 2.37 1.42 1.52 1.58 D.sub.120' (in NM)
8.49 12.53 10.07 13.47 13.88 12.38 D.sub.120' - D.sub.min (in NM)
6.58 11.18 7.70 12.05 12.36 10.80 ##STR1## 16.5 8.2 11.1 6.5 7.7
10.3 Mooney rest (DIN 53 523/24) ML 4 (100.degree. C.) 155 122 172
124 127 132 t.sub.5 (130.degree. C.) 70 83.7 60.0 61.7 64.1 85.4
__________________________________________________________________________
The figures representing the test results show the following. By
adding 7.5 parts by weight of 3-chloropropyl triethoxy silane to
the comparison or control mixture V4.1, the following improvements
are obtained: increase in tensile strength, remarkable increase in
moduli and Shore hardness and improvement in abrasion or wear
(V4.2). As expected, slight improvements in the properties of the
vulcanisates are also obtained by the addition of carbon black. The
Rheometer values are also improved to some extent whereas--again as
expected--Mooney viscosity is impaired (V4.3 compared with V4.1).
If, now the silane is added (see V4.4 compared with V4.3), the (in
some cases very distinct) improvements again occur, except there is
no increase in tensile strength.
However, if now the preparations according to the invention (see
E4.1 and E4.2) are used instead of the separate individual
additions, further improvements in the moduli and cross-link
density surprisingly occur both in the black mixture and also in
the white mixture. These synergistic effects were confirmed after
the preparations had been stored for two months, which is
indicative of high stability in storage of the preparations
according to the invention.
Example 5
The following mixtures based on silica-filled
poly-2-chloro-1,3-butadiene (Bayprene 210, a product of Bayer AG)
were prepared and tested:
______________________________________ Quantities in the mixtures
V5.1 V5.2 E5.1 ______________________________________ Constituents
Polychlorobutadiene 100.0 100.0 100.0 Magnesium oxide, light 4.0
4.0 4.0 Silica filler (see Example 2) 40.0 40.0 38.0 Cl-PTES -- 2.0
-- Preparation of equal parts of Cl-PTES and silica filler (see
above) -- -- 4.0 Naphthenic plasticiser oil (setting point -
28.degree. C.) 15.0 15.0 15.0 Ethylene thiourea 0.75 0.75 0.75 Zinc
oxide (Read Seal Quality) 5.0 5.0 5.0 Test Results: Tensile
strength (in MPa) 11.7 11.4 16.2 Modulus 300 (in MPa) 5.4 10.2 11.1
Breaking elongation (in %) 540 320 390 Rheometer Test D.sub.max
-D.sub.min (in Nm) 7.50 9.63 13.10
______________________________________
The test results of Example 5 also demonstrate the superior effect
of the preparation according to the invention (E5.1) in relation to
the separate addition of the constituents of the preparation in
equal quantities (V5.2) and in relation to the control mixture
(V5.1).
Example 6
If, in the mixtures of Example 5, the silica filler is supplemented
by a clay (Suprex Clay, a product of J. M. Huber Corp., Locust,
N.J., U.S.A.), the required improvements are also obtained (see
following Table). Synergistic effects could also be observed in the
case of the clay-filled mixture.
______________________________________ Quantities in the mixture
V6.1 V6.2 E6.1 ______________________________________ Constituents
Polychlorobutadiene (see example 5) 100.0 100.0 100.0 Magnesium
oxide, light 4.0 4.0 4.0 Silica filler 40.0 40.0 40.0 Suprex Clay
-- 11.3 -- Preparation according to Example 3 (Cl-PTES and Suprex
Clay) -- -- 13.3 Naphthenic plasticiser oil (setting point -
28.degree. C.) 15.0 15.0 15.0 Ethylene thiourea 0.75 0.75 0.75 Zinc
oxide (Red Seal Quality) 5.0 5.0 5.0 Test Results: Tensile strength
(in MPa) 16.0 14.7 17.7 Modulus (in MPa) 5.0 6.0 12.1 Breaking
elongation (in %) 670 620 430
______________________________________
Industrial applications for the rubber mixtures of moulding
compositions and their vulcanisates are, for example, industrial
rubber articles such as cable sheaths, hoses, heating tubes, also
electrical insulations, linings, impregnations and coatings of
heat-resistant fabrics, particularly drive belts, V-belts, conveyor
belts, roll coverings, seals, tyres, particularly tyre treads, as
well as shoe soles, damping and vibration elements and similar
articles.
The entire disclosure of German priority application No. P 29 33
346.8-43 is hereby incorporated by reference.
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